Comparative analysis of the CO 2 capture properties for pure, K- and

Na-doped Li 5 AlO 4 .
M. Teresa Flores-Martínez and Heriberto Pfeiffer
Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Circuito
Exterior s/n, Ciudad Universitaria, Del. Coyoacán, CP 04510 México, Ciudad de México.,
trflores@unam.mx

Introduction
CO 2 is the main anthropogenic greenhouse gas in the atmosphere. One of the environment
impacts of the large amount of CO 2 in the atmosphere is the global warning and climate
change.[1] Most efforts are focused mainly on reducing the amount of CO 2 emitted to the
atmosphere.[2] Recently, considerable high interest has been developed in the lithium-based
ceramics and other alkaline elements due to their high CO 2 absorption capacity at elevated
temperatures. Among these ceramics, Li 5 AlO 4 seems to be one of the best possible options
as a CO 2 capture material because of its high theoretical CO 2 chemisorption capacity (15.9
mmol/g).[3]
Previously, some works have reported the CO 2 chemisorption process on Na- and K-doped
lithium ceramics, where the capture processes are increased considerably, in comparison
with their respective pristine ceramics. This behavior has been explained because lithium
carbonate, formed during the CO 2 chemisorption, forms an eutectic mixture with either
potassium or sodium carbonates. Thus the ceramic surface is partially fused favoring the
diffusion processes.[4,5]
This work describes the CO 2 chemisorption process in K− or Na−doped β−Li 5 AlO 4 systems
under different thermal conditions. Furthermore, different CO 2 sorption kinetic studies were
performed on K- or Na-doped lithium aluminates and the reaction mechanism was evaluated.

Experimental Details
β−Li 5 AlO 4 was synthesized using a solid-state reaction that employs lithium oxide (Li 2 O) and
gamma alumina (γ−Al 2 O 3 ). It was characterized by X-ray diffraction (XRD), scanning electron
microscopy (SEM) and N 2 adsorption. Doped powders of β−Li 5 AlO 4 were mechanically
mixed with 10 wt% of potassium (K 2 CO 3 ) or sodium (Na 2 CO 3 ) carbonate. These samples
were labeled as m−K−β−Li 5 AlO 4 and m−Na−β−Li 5 AlO 4 , respectively. Additionally, Na− and
K−doped β−Li 5 AlO 4 samples were synthesized by a solid-state reaction, adding 10 wt% of
potassium or sodium carbonate during the synthesis process. In these cases, the samples
were labeled as s−K−β−Li 5 AlO 4 and s−Na−β−Li 5 AlO 4 , respectively.
To determine the CO 2 chemisorption capacity, the Na and K−doped lithium aluminates were
analyzed thermogravimetrically in the presence of dry CO 2 . Initially the samples were
dynamically heated from room temperature up to 900 °C at 5 °C/min, subsequently the
samples were tested isothermally at different temperatures (from 400 to 700 °C) under the
presence of a CO 2 flow (60 mL/min). For the isothermal experiments, the samples were
heated up to the corresponding temperature under a N 2 flow. Once the desired temperature
was reached, the gas flow was switched from N 2 to CO 2 .

Results and Discussion

The formation of β−Li 5 AlO 4 was confirmed by X-ray powder diffraction (XRD, data not
shown). The surface area of ceramics with and without K or Na doping was determined using
the BET model [6]. The obtained values were considerably low (>1 m2/g), thus, it was
assumed that they had no influence on the CO 2 capture.
Initially the CO 2 chemisorption capacities of Na- and K-doped β−Li 5 AlO 4 were analyzed
thermogravimetrically in the presence of a CO 2 flux. Figure 1 shows the dynamic
thermograms obtained for Na − and K−doped β−Li 5 AlO 4 , compared with the β−Li 5 AlO 4
pristine. These thermograms show two different processes taking place in the materials. The
first one is a superficial CO 2 chemisorption process occurring between ~200 and ~400 °C.
Then, when the temperature was increased (>500 °C), the diffusion processes were
activated and the reaction continued through the bulk of the material, completing the CO 2
chemisorption (Eqn (1)). Similar thermal trends have already been observed for other lithium
ceramics [7−9]. Depending of the Na and K addition way, two different trends were observed.

Li 5 AlO 4 (s) + 2 CO 2 (g) 2 Li 2 CO 3 (s) + LiAlO 2 (s) (1)

170 β−Li5AlO4
165 s-10K-β−Li5AlO4
160 m-10K-β−Li5AlO4
s-10Na-β−Li5AlO4
155
m-10Na-β−Li5AlO4
150
145
140
Weight (%)

135
130
125
120
115
110
105
100

100 200 300 400 500 600 700 800 900

Temperature (°C)

Figure 1. Comparative dynamic thermogravimetric analyses of Na- and K-containing β−Li 5 AlO 4
samples with pure β−Li 5 AlO 4 sample into a CO 2 flux.

Then, in order to analyze and understand the K- and Na-doping effects in β−Li 5 AlO 4 ,
different and independent isothermal experiments were performed. The CO 2 chemisorption
of s−K−β−Li 5 AlO 4 showed an exponential behavior between 400 and 500 °C (Figure 2). The
eutectic mixtures should be produced at temperatures around to 550 °C, improving the CO 2
diffusion-controlled chemisorption process. Additionally, it was possible to observe a double
process occurring at 650 °C, the first one taking place during the first minutes, and the
second one happening at longer times. This isothermal behavior is consistent with the
observation of a double chemisorption mechanism mentioned above. Finally, the
intercrystalline diffusion processes were activated at 700 °C, improving even more the CO 2
chemisorption.
After the qualitative analysis, the isotherms were fitted to a first-order reaction model with
respect to Li 5 AlO 4 (Eqn (1)). ln[Li 5 AlO 4 ] = -kt (2)
where k is the reaction rate constant, t is the time, and [Li 5 AlO 4 ] is the molar concentration of
the ceramic (Figure 3).
 s-10K-β−Li5AlO4
170
700 °C
160
650 °C
150
Weight (%)

140

130
600 °C

120
550 °C

110 500 °C 450 °C

400 °C
100
0 20 40 60 80 100 120 140 160 180
Time (min)

Figure 2. CO 2 isotherms of s−K−β−Li 5 AlO 4 at different temperatures.

ln [Li5AlO4] =-k t
0.025
β−Li5AlO4
s-10K-β−Li5AlO4
0.020 m-10K-β−Li5AlO4
s-10Na-β−Li5AlO4
m-10Na-β−Li5AlO4

0.015
k (s-1)

0.010

0.005

0.000

400 450 500 550 600 650 700

Temperature (°C)

Figure 3. Comparison of plots of k versus Temperature, for the data obtained at kinetic analysis,
assuming a first-order reaction of Li 5 AlO 4 for short times.

If the reaction is controlled by the interface movement from the surface inward it can be
described by the following equation: 1-(1-α)1/3 = k D t (3)
where α is the molar fraction of Li 2 CO 3 produced, t is time and k D is a constant which
depends on the diffusion coefficient, particle size, and temperature (Figure 4).

Eyring's model, is typically used on heterogeneous reactions and solid−gas system to

describe this kind of temperature dependence diffusion processes, then k and k D were to
Eyring's model. ln(k i /T) = -(∆H‡/R)(1/T) + lnE + ∆S‡/R (4).
Thus, by means of fit the data obtained to a linear model, the activation enthalpies (ΔH‡)
were calculated for both different processes (Tables 1 and 2), for at least two temperature
ranges. ΔH‡ values for CO 2 direct chemisorption are lower in K- and Na-containing samples
compared to the β−Li 5 AlO 4 pure sample. These values are higher for the kinetically
controlled chemisorption processes. It means that the direct chemisorptions process is less
dependent of temperature for doped samples than without doping. In the kinetically
controlled chemisorption case it could be observed the opposite behavior. This implies that
the direct chemisorption process is less temperature dependent than the chemisorption
process kinetically controlled by diffusion processes.
 kD t = 1-(1-α)1/3
β−Li5AlO4
s-10K-β−Li5AlO4
1,0x10-5 m-10K-β−Li5AlO4
s-10Na-β−Li5AlO4
m-10Na-β−Li5AlO4
8,0x10-6

6,0x10-6
kD (s-1)

4,0x10-6

2,0x10-6

0,0

400 450 500 550 600 650 700

Temperature (°C)

Figure 4. Comparison of plots of k versus Temperature, for the data obtained at kinetic analysis,
assuming a diffusion mechanism controlled by the interface movement from the surface inward.
‡
Table 2. The activation enthalpies (ΔH ) for
‡
Table 1. activation enthalpies (ΔH ) for the diffusion mechanism controlled by the
CO 2 direct chemisorption interface movement from the surface inward
ΔH (kJ/mol) ΔH (kJ/mol)
‡ ‡
Sample (450 - 650 °C) Sample (400 - 550 °C)
β−Li 5 AlO 4 69.0 β−Li 5 AlO 4 34.0
m-10K-β−Li 5 AlO 4 48.5 m-10K-β−Li 5 AlO 4 56.1
m-10Na-β−Li 5 AlO 4 30.2 m-10Na-β−Li 5 AlO 4 112.2
s-10K-β−Li 5 AlO 4 66.2 s-10K-β−Li 5 AlO 4 60.8
s-10Na-β−Li 5 AlO 4 43.5 s-10Na-β−Li 5 AlO 4 70.1

Conclusion
It was observed that the Na and K-doped β−lithium aluminate, in the process of
chemisorption of carbon dioxide at high temperatures, present an improvement in the CO 2
capture process in the temperature range from 450 to 650 °C. However, the mechanically
doped samples exhibit a great improvement in the CO 2 capture temperature range from 500
to 650 °C. Thus, the possible application of each sample may depend on the temperature.
Overall, the CO 2 capture capacity from Na or K-doped β−Li 5 AlO 4 is good considering their
small surface area.

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Acknowledgements
This work was financially supported by PAPIIT and SENER-CONACYT. M. T. Flores-Martínez thanks
PAPIIT and CONACYT for personal financial support.